CN112611747A - Method for quantitatively analyzing influence of metal ions in catalyst layer of proton exchange membrane fuel cell on performance of proton exchange membrane fuel cell - Google Patents
Method for quantitatively analyzing influence of metal ions in catalyst layer of proton exchange membrane fuel cell on performance of proton exchange membrane fuel cell Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/389—Measuring internal impedance, internal conductance or related variables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a method for quantitatively analyzing the influence of metal ions in a catalyst layer of a proton exchange membrane fuel cell on the performance of the proton exchange membrane fuel cell, belonging to the technical field of fuel cells. The method comprises the following steps: respectively and uniformly spraying metal salt solution on the cathode catalyst layers of 5 CCM electrodes to ensure that the doping amount of metal ions on the cathode catalyst layers of the CCM electrodes is 0.1mg/cm2、0.01mg/cm2、0.005mg/cm2、0.001mg/cm2、0.0001mg/cm2And assembling 5 single cells, and performing performance test on the 5 single cells to obtain a relation curve of the metal ion doping amount and the battery performance change. The invention adopts a spraying method to prepare doped metalThe ionic catalyst layer electrode is simple to operate, high in reliability and wide in applicability, is suitable for quantitative analysis of the influence of different metal ions on the performance of the fuel cell, and provides an important reference basis for the service life test of the fuel cell and the material type selection of parts.
Description
Technical Field
The invention relates to a method for quantitatively analyzing the influence of metal ions in a catalyst layer of a proton exchange membrane fuel cell on the performance of the proton exchange membrane fuel cell, belonging to the technical field of fuel cells.
Background
Proton Exchange Membrane Fuel Cells (PEMFC) have the characteristics of high energy conversion efficiency, high response speed, good low-temperature starting performance, no pollution, low emission and the like, have very wide application prospects in the fields of fixed power stations, standby power supplies, transportation, aerospace, military industry and the like, and are particularly concerned about the application in the aspect of fuel cell automobiles, so the research and development of related technologies of PEMFC also become a research hotspot of global attention.
At present, the durability of the proton exchange membrane fuel cell is the key of the commercial popularization of the proton exchange membrane fuel cell and is also the difficulty of material technology breakthrough and practical application. The frequent load change, open circuit/idling, start-stop and other operation conditions of the vehicle are the main reasons for the reduction of the service life of the fuel cell. Under these complicated operating conditions, the fuel cell often has phenomena of high and low temperature shift, dry and wet cycle, high and low potential shift, reverse polarity, etc., which causes the degradation of the cell performance, for example: (1) a decrease in the electrochemically active area due to agglomeration, migration, or catalyst poisoning of catalyst particles; (2) a decrease in proton conductivity caused by contamination of the proton exchange membrane or catalytic layer; (3) loss or degradation of polytetrafluoroethylene in the diffusion layer, and increased mass transfer resistance caused by structural change of the microporous layer.
In the existing material system, due to the use of metal bipolar plates and metal parts, various metal ions are inevitably introduced into the battery, and once the metal ions enter the membrane electrode, irreversible physical and chemical attenuation occurs on a proton exchange membrane and a catalytic layer, so that the proton conductivity, the gas permeability and the like of the battery are directly influenced, and the output performance and the stability of the battery are influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for quantitatively analyzing the influence of metal ions in a catalyst layer of a proton exchange membrane fuel cell on the performance of the proton exchange membrane fuel cell. According to the invention, quantitative metal ions are directly and uniformly sprayed on the catalyst layer, the doping amount is calibrated by an inductively coupled plasma emission spectrometer (ICP) instrument, and the performance of a single cell is tested, so that a relation curve between the concentration of the metal ions and the performance of the cell can be accurately obtained, and quantitative analysis is realized.
The method comprises the following steps:
(1) evenly spraying catalyst slurry on one side of a proton exchange membrane, wherein the loading capacity of the catalyst slurry on the proton exchange membrane is 0.2mg/cm2To obtain the anode of the CCM electrode, and then evenly spraying the catalyst slurry on the other side of the proton exchange membrane, wherein the loading capacity of the catalyst slurry on the proton exchange membrane is 0.4mg/cm2Obtaining the cathode of the CCM electrode;
(2) respectively and uniformly spraying metal salt solution on the cathode catalyst layers of 5 CCM electrodes to ensure that the doping amount of metal ions on the cathode catalyst layers of the CCM electrodes is 0.1mg/cm2、0.01mg/cm2、0.005mg/cm2、0.001mg/cm2、0.0001mg/cm2；
(3) Assembling CCM electrodes with different doping amounts of metal ions, a gas diffusion layer and a fuel cell test fixture into 5 monocells respectively;
(4) and (5) carrying out performance test on the single cells to obtain a relation curve of the metal ion doping amount and the battery performance change.
Preferably, the spraying in step (2) is: and fixing the CCM electrode at a position 1-2cm above the heating device, and spraying the cathode catalyst layer of the CCM electrode.
Preferably, the heating temperature of the heating device is 80-90 ℃.
Preferably, the spraying rate is 0.5-1 μ L/s
Preferably, the metal salt in the metal salt solution is copper salt, iron salt, nickel salt, chromium salt, sodium salt, calcium salt, potassium salt, aluminum salt, lithium salt or cobalt salt.
The invention has the following beneficial effects:
(1) the invention adopts the spraying method to prepare the catalytic layer electrode doped with metal ions, and has simple operation and high reliability.
(2) The method has wide applicability, and is suitable for quantitative analysis of the influence of different metal ions on the performance of the fuel cell.
(3) The method obtains the relation curve of the polarization performance of the battery and the metal ions with different doping amounts, obtains the relation of the doping amount of the metal ions and the performance change of the battery, and has important significance for the model selection and the service life test research of the core material of the fuel battery.
(4) The invention combines electrochemical characterization means such as polarization performance, cyclic voltammetry performance, oxygen reduction performance, alternating current impedance, hydrogen permeation current, catalytic layer proton conduction resistance test and the like, comprehensively analyzes the influence of different metals and doping amounts thereof on the battery performance, finds out the main contradictions influencing the battery performance, explores the mechanism and provides an important basis for effectively solving the problem of performance attenuation caused by the influence of metal ions on the fuel battery.
Drawings
Fig. 1 is a schematic view of a unit cell assembly structure of example 1;
FIG. 2 is a cell polarization performance test curve of example 1;
FIG. 3 is a test curve of cyclic voltammetry performance of a single cell of example 1;
FIG. 4 is a graph of specific cell mass activity of example 1;
FIG. 5 is a single cell AC resistance test curve of example 1;
fig. 6 is a graph of a cell hydrogen permeation current test of example 1;
FIG. 7 is a proton conductivity resistance test curve for the single cell catalytic layer of example 1;
fig. 8 is a graph of the cell performance decay rate test of example 1.
Detailed Description
The following describes embodiments of the present invention in detail. The following described embodiments are exemplary only, and are not to be construed as limiting the invention.
Example 1
(1) Taking a square proton exchange membrane with the side length of 5cm, and uniformly spraying catalyst slurry on one side of the proton exchange membrane with the spraying area of 25cm2The loading capacity of the catalyst slurry on the proton exchange membrane is 0.2mg/cm2To obtain the anode of the CCM electrode, and then evenly spraying the catalyst slurry on the other side of the proton exchange membrane with the spraying area of 25cm2The loading capacity of the catalyst slurry on the proton exchange membrane is 0.4mg/cm2Obtaining the cathode of the CCM electrode;
(2) 4.89g of CuSO were weighed4·5H2Dissolving O powder in deionized water, stirring and dispersing for 2h to fully dissolve the O powder, and then performing constant volume by using a 1L volumetric flask, wherein the concentration is 1.25%;
(3) fixing the CCM electrode at a position 2cm above the heating device, with the cathode facing upward, heating at 90 deg.C, extracting 20ml of the solution prepared in step (2) in a spray gun, uniformly spraying the solution on the cathode catalyst layer of the CCM electrode at a spraying rate of 0.8 μ L/s to make the doping amount of the solution on the catalyst layer 0.1mg/cm2、0.01mg/cm2、0.005mg/cm2、0.001mg/cm2、0.0001mg/cm25 copper ion CCM electrodes with different doping amounts are manufactured;
(4) fixing an anode end plate with a heating sheet on the outer side by using a fixing bolt, and then sequentially stacking an insulating pad, an anode current collecting plate, an anode graphite pole plate with a direct current field, a sealing pad, a polyester frame, an anode gas diffusion layer, CCM electrodes loaded with metal ions with different doping amounts, the polyester frame, a cathode gas diffusion layer, the sealing pad, a cathode graphite pole plate with the direct current field, a cathode current collecting plate, an insulating pad and a cathode end plate, wherein after all the components are stacked, screws are screwed tightly, the torque is 4-6N, and the screws are required to be screwed tightly according to the diagonal sequence when being screwed tightly, so that the uniform stress of the battery in the assembly process is ensured as much as possible, and 5 CCM single cells are assembled;
(5) the 5 copper ion single cells, the undoped copper ion single cells and the doped deionized water single cells obtained in the above manner with different doping amounts were subjected to polarization performance tests using a 850e-885 fuel cell test system. Hydrogen/air is used as reaction gas, the hydrogen metering ratio and the air metering ratio are both 2, the battery operation temperature is 80 ℃, the cathode humidification temperature and the anode humidification temperature are both 80 ℃, the battery operation pressure is not backpressure, the current output is controlled by adjusting the electronic load, the voltage value is recorded, and each current density point stably operates for 5 min. Polarization curve performance was tested as shown in fig. 2;
(6) the obtained 5 copper ion single cells with different doping amounts, the un-doped copper ion single cell and the doped deionized water single cell are subjected to cyclic voltammetry performance tests by using a 850e-885 fuel cell testing system. The cathode side of the battery is introduced with humidified N2The electrochemical activity area change is further calculated by calculating the integral area of a hydrogen desorption area through the obtained cyclic voltammetry curve as shown in figure 3(a) so as to be shown in figure 3 (b);
(7) the above obtained 5 copper ion single cells with different doping amounts were subjected to an oxygen reduction performance test using a 850e-885 fuel cell test system. Hydrogen/oxygen is used as reaction gas, the hydrogen metering ratio and the oxygen metering ratio are both 2, the operation temperature of the battery is 80 ℃, the humidifying temperature of a cathode and an anode is 80 ℃, the operation pressure of the battery is not backpressure, the current output is controlled by adjusting an electronic load, the voltage value is recorded, each current density point stably operates for 15min, the oxygen reduction performance test is carried out, and finally, the dynamic current under the potential of 0.9V is obtained by combining a Tafel formula according to the oxygen reduction curve, so that the quality specific activity of the battery is obtained, as shown in figure 4;
(8) the above obtained copper ion sheets with 5 different doping amounts were subjected to the 850e-885 fuel cell test systemAnd performing alternating current impedance performance test on the battery, the single battery without doped copper ions and the single battery with doped deionized water. Hydrogen/oxygen is used as reaction gas, the metering ratio of hydrogen to oxygen is 2, the operation temperature of the cell is 80 ℃, the humidifying temperature of the cathode and the anode is 80 ℃, the operation pressure of the cell is not back pressure and is respectively 100mA/cm2、800mA/cm2、1200mA/cm2、1600mA/cm2Performing full-frequency impedance test on the points, wherein the frequency range is 0.1-10000Hz, fitting an EIS curve through an equivalent circuit, and further obtaining ohmic impedance, activation impedance and mass transfer impedance under different densities, as shown in FIG. 5, and obtaining impedance values according to the impedance spectrum fitting through the equivalent circuit, which are shown in Table 1;
(9) the obtained 5 copper ion single cells with different doping amounts, the non-doped copper ion single cell and the doped deionized water single cell were subjected to a hydrogen permeation current test by using an 850e-885 fuel cell test system. Introduction of N into the cathode2Anode is introduced with H2The gas flow rates of the cathode and the anode are both 200ml/min, the gas humidification temperature is 80 ℃, the cell operation temperature is 80 ℃, the cell system is subjected to a hydrogen permeation current test, the potential scanning range is 0.09-5.40V, the scanning speed is 50mV/s, and the gas permeability of the proton exchange membrane is evaluated by comparing the hydrogen permeation current corresponding to 0.45V, as shown in figure 6;
(10) and (3) carrying out catalytic layer proton conduction resistance tests on the 5 copper ion single cells, the undoped copper ion single cells and the doped deionized water single cells with different doping amounts obtained by the AUTOLAB electrochemical workstation. Introduction of N into the cathode2Anode is introduced with H2The cathode and anode gas flow rates are all 200ml/min, the gas humidification temperature is 80 ℃, the battery operation temperature is 80 ℃, the catalyst layer proton conduction resistance test is carried out on the battery system, and the influence of metal impurity ions on the catalyst layer proton conduction performance is researched, as shown in fig. 7;
(11) the performance test results of the single cell are analyzed, and single cell performance decay rate curves with different copper ion doping amounts are obtained, as shown in fig. 8.
As can be seen from FIG. 2, the polarization performance of the single cell gradually increases with the increase of the doping amount of copper ions in the cathode catalyst layerThe reduction and the performance attenuation are gradually increased, which shows that the copper ions have a significant influence on the overall performance of the fuel cell. The main reasons can be divided into the following two points: doping of copper ions can affect the water balance and proton conductivity of a proton exchange membrane in the membrane electrode; copper ions can replace protons in the proton exchange membrane to occupy the position of the sulfonate group, so that the combination of water and the sulfonate group can be seriously hindered, the water migration number in the membrane is increased, the water content is rapidly reduced, the membrane is rapidly shrunk after water shortage, the proton migration number is further reduced, the ionic conductivity is reduced, and the overall performance of the cell is reduced; furthermore, if the copper ions and the battery intermediate phase product H are generated during the operation of the battery2O2When coexisting, the proton exchange membrane can be seriously degraded, and the phenomena of membrane thinning, surface roughness, cracks, pin holes and the like are caused, so that the proton conductivity, the gas permeability and the stability of the membrane are directly influenced. ② the doping of copper ion will affect the proton conductivity and oxygen reduction performance of the catalyst layer in the membrane electrode. The membrane electrode catalyst layer is generally composed of a catalyst and a carrier thereof, a polymer and pores, electrode reaction mainly occurs in a three-phase reaction interface area in a micro-scale range, and electron conduction in the catalyst carrier, ion migration in the polymer and mass transfer in a reactant/product electrode pore channel respectively occur in three phase states, wherein the polymer mainly plays roles of proton conduction and adhesion, and the chemical structure of the polymer is consistent with that of a proton exchange membrane and is also easily influenced by copper ions, so that the proton conduction capability of the polymer is reduced. In addition, copper ions can seriously hinder the oxygen reduction kinetics and the oxygen transfer process at the interface of the polymer phase and the catalyst, thereby influencing the electrochemical reaction and the performance of the battery.
As can be seen from fig. 3, as the doping amount of copper ions in the cathode catalyst layer increases, the specific mass activity of the battery gradually decreases, indicating that the oxygen reduction performance of the battery gradually decreases; the mass of the battery increases linearly with the decrease of the copper ion concentration in the cathode catalyst layer.
As can be seen from FIG. 4, as the doping amount of copper ions increases, the mass specific activity of the battery gradually decreases as the copper ions are dopedThe concentration of the seed is less than or equal to 0.001mg/cm2When the mass specific activity of the battery is almost the same as that of the standard sample, the result shows that the concentration of copper ions is less than or equal to 0.001mg/cm2When the concentration of copper ions is more than 0.001mg/cm, the influence on the quality and specific activity of the battery is small2The battery quality gradually increases with the decay of the specific activity performance.
As can be seen from fig. 5, the impedance spectrum was divided into ohmic impedance, activation impedance, and mass transfer impedance according to the conventional equivalent circuit of the fuel cell and fitted to obtain the values of table 1. When the concentration of copper ions is more than or equal to 0.001mg/cm2When the concentration of the copper ions is less than or equal to 0.001mg/cm, the ohmic resistance is remarkably increased with the increase of the concentration of the copper ions2The ohmic impedance is comparable to the standard; the activation impedance is greatly influenced by the concentration of copper ions, and the ohmic impedance is linearly increased along with the increase of the concentration of the copper ions; the mass transfer impedance is less affected by the copper ion concentration.
As can be seen from fig. 6, the results of the single cell hydrogen permeation current tests of different copper ion doped catalyst layers are not very different, which indicates that the influence of the introduction of copper ions in the catalyst layers on the gas permeability of the proton exchange membrane is small in a short time.
As can be seen from FIG. 7, the proton resistance of the catalytic layer gradually increased with the increase of the doping amount of copper ions, and the doping amount was 0.01mg/cm2A remarkable turning point appears when the doping amount of the copper ions is 0.1mg/cm2In this case, the catalytic layer has a proton conduction resistance as high as 11.19 m.OMEGA. The increase of proton conduction resistance of the catalyst layer is the main reason of the performance attenuation of the battery, and the introduction of copper ions causes irreversible chemical attenuation to the catalyst layer polymer, thereby greatly reducing the proton conduction capability of the catalyst layer polymer, and hindering the establishment of three interfaces, thereby influencing the progress of the hydrogen-oxygen electrochemical reaction.
As can be seen from fig. 8, the cell performance decay rate linearly increases with the increase in the amount of copper ion doping in the cathode catalyst layer, and the decay rate increases as the current density increases. The higher the doping amount of copper ions, the lower the proportion of the sites occupying the sulfonate groups, the higher the proton conduction resistance of the cell, and therefore, the higher the decay rate of the performance.
The above examples are merely preferred embodiments of the present invention, and are not intended to limit the embodiments. The protection scope of the present invention shall be subject to the scope defined by the claims. Other variations and modifications may be made on the basis of the above description. Obvious variations or modifications of this invention are within the scope of the invention.
TABLE 1
Claims (5)
1. A method for quantitatively analyzing the influence of metal ions in a catalyst layer of a proton exchange membrane fuel cell on the performance of the proton exchange membrane fuel cell is characterized in that: the method comprises the following steps:
(1) evenly spraying catalyst slurry on one side of a proton exchange membrane, wherein the loading capacity of the catalyst slurry on the proton exchange membrane is 0.2mg/cm2To obtain the anode of the CCM electrode, and then evenly spraying the catalyst slurry on the other side of the proton exchange membrane, wherein the loading capacity of the catalyst slurry on the proton exchange membrane is 0.4mg/cm2Obtaining the cathode of the CCM electrode;
(2) respectively and uniformly spraying metal salt solution on the cathode catalyst layers of 5 CCM electrodes to ensure that the doping amount of metal ions on the cathode catalyst layers of the CCM electrodes is 0.1mg/cm2、0.01mg/cm2、0.005mg/cm2、0.001mg/cm2、0.0001mg/cm2；
(3) Assembling CCM electrodes with different doping amounts of metal ions, a gas diffusion layer and a fuel cell test fixture into 5 monocells respectively;
(4) and (5) carrying out performance test on the single cells to obtain a relation curve of the metal ion doping amount and the battery performance change.
2. The quantitative analysis method according to claim 1, characterized in that: the spraying method in the step (2) comprises the following steps: and fixing the CCM electrode at a position 1-2cm above the heating device, and spraying the cathode catalyst layer of the CCM electrode.
3. The quantitative analysis method according to claim 2, characterized in that: the heating temperature of the heating device is 80-90 ℃.
4. The quantitative analysis method according to claim 3, characterized in that: the spraying rate is 0.5-1 mu L/s.
5. The quantitative analysis method according to claim 4, characterized in that: the metal salt in the metal salt solution is copper salt, iron salt, nickel salt, chromium salt, sodium salt, calcium salt, potassium salt, aluminum salt, lithium salt or cobalt salt.
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